Condensate of biurea with carboxylic acids



United States P t nt M Cg Patented Mar. 7, 1961 'CONDENSATE F BIUREA WITH tubes)v at atmospheric pressure. After attainingaitein F. Grillot and Vivian T. Stannett,"Syracuse; N.Y'., as-

signors to W. R. Grace & (30.; New. York, N.Y.,.a' corporation of Connecticut No Drawing. Filed Feb. 20, lsss ser. No. 516.230

This invention relates to a new method of preparing a resin. More specifically it pertains to amethod of pre paring a resin from biurea and a linear aliphatic dicarboxylic acid having a chain length of, at least 3. Additionally that invention includes novel biurea-dicarboxylic acid. reaction products in a resinous form.

In essence the invention embodies heating together biurea (H NCONHNHCONH and a linear aliphatic dicarboxylic acid having a chain length of at least 3 at atmospheric pressure and thereby forming a resin which on cooling results in a clear hard vitreous product.

The prior art teaches that polycondensation products can; be obtained by reacting under pressurebiureaand its derivatives with dicarboxylic acids having achain length of at least 6; see German Patent 745,473 to Moldenhauerret al. issued March 13. 1944. The product obtained is said to be suited forproduction, of fibers and In evaluating Moldenhauers work, we have found that the anhydrides used by Moldenhauer at superatmospheric pressure are not operative at atmospheric pressure to form; resins with biurea. It is therefore. surprising that the reaction of biurea and a linear aliphatic, dicarboxylic acid-having a chain length of at least 2; will yielda clear resinousproductat atmosphericpressure. V V

The biurea:dicarboxylic acid mole ratiocanbe in the n nfvl q o The addition of a minor amount ofan acid catalyst, such as p-toluene sulfonic acid, reduces the: reaction time considerably but has no noticeable effecton'the resinous product.

The following general procedure was used to make the novel resins. One mole of biurea and onemole of a dicarboxylic acid were intimately mixed together with an acid catalystsucli asp-toluene sulfonic acid? to there):- tent of 0.1% by weight of reactants employed and quickly heated by meansof an oil bath to atemperature in the range of ZOO-250 C. The acidcatalyst is not necessary, but accelerates the reaction. The reactions peratureinthe range of 2005 250" C. some productbegins to form within seconds, and thefreactipnjisj'generally complete in 30-40 minutes. However, Ionggerreacti'oii 5 times,j ,e:g-., sci/feral hours; may be u'sed desired, 1' but Cornelius Sherman Grave, gi j otter little or'no advantage. 'A"vigorous;foamingusually TABLE rI-nEAoTmNs OFABIIITDIEEXWITH DICARBOXYLIC Biureaz. Wt. used=0.354 l Mole ratio, biurea:acid=1 [0.1% p-toluene sulfonic acid used as catalyst, based on weight. of reactants] Acid Weight, Remarks Malenic 0.312 S1. yellow liquid formed in"30.min.st

220240 C. A clear slightly reddish- V yellliiigv resinous product formed on coo g. Succinie 0. 354 7 Dark amber liquid formed in about'l0 min. at 230 C. Clear dark amber resinous product resulted. Glutaric 0.396 Clear solution formed in 15 min. at 230 C.-

Clela r1 almost colorless solid formed on coo g. Adipic 0. 438 Clear amber liquid in 28 min. at 220-230 C. Clear light'to medium amber resinous product resulted. Pimellc 0. 480 Clear pale gold colored solution formed in 30 min. at 230 C. Clear yellow-red solid formed upon cooling. Azelaic 0; 564 Clear solution formed in 30 min. at 230 0.

' i(glear resin-like solid formed upon coolg. Bebacic 0.606 Dark amber liquid in 30 min. at 220-240 0. Oleafieddark amber resinous product res a a e a solvent and visible solubility was again recorded. at a third observation as to solubility was made after the tube was removed from the oil bath and cooledback down to room temperature. Table II shows the results ofithe solubility tests of the novel resins in various solvents were performed in heat-resistant glass tubes (e.g., Pyrex '55 under the conditions specified supra.

TABLE IL-SOLUBILI'IIES onrnonuo'rs FORMED FROM THE REACTION or BIULREA WITH THE some.

7 V g V ING DICARBOXYLIC ACIDS V {Samples consist 010.05 gm. of product per 1.5 cc. solvent],

Solvent Malonie Succinic Glutarlo Adipio Pimelie Azelaic sebaei Toluene: p a

Room Tem in nl insol--.. insoL--- insol B. Pt insol insol insol. ins After Cooling lnsol; insol-...- ins Butyl'Alcohol:

Room Tem winsol .insoL"- lnsol- Pt. insol' 'insol.--- insol..--

TABLE H.-Oontlnued Solvent Malonio Succinic Glutraio Adipio Pimelio Azelaio Sebaclo After Cnnlin insol. lnsnl insol...- insol insol insol insol. Methyl Ethyl:

Room Temp lnsol insoL-.- insoL.-. .Pt insol insol---. insol..-.. After Gooling. insol. 111501.-.- insol ioxane: Room Temp insol.eolor inso1-.- insol insol lnsol.

change. t insoL-.. insol insol. After Cooling insol ins insol--- lnsol. chloroform:

Room T p insol. insol. insol insol. Pt insol insoL--- ins insol. After Oooling insol ins ins Dimethyliormamid Room Temp..- suspension sol sol insol.

forms. B. Pt suspension sol sol sol.

forms. After Cooling. suspension sol sol.. insol-... lnsol. forms. H

Room Temp sLsol sol sol sol., s1. insol.

cloudy. B. Pt sol sol sol so1..-- insol. After Cooling s1. sol sol sol sol insol. Methyl Alcohol:

Room Temp insol sol sol o1- lnsol. t insol sol sol insol insol. After Cooling insol sol sol lnsol. lnsol.

Softening point temperature ranges as shown in Table III were determined by the following general procedure. Solid resinous product was placed in a heat-resistant test tube (e.g., Pyrex tube) and heated slowly in an oil bath. The softening point range was designated as the temperature range between the first sign of softening and the temperature range at which the whole mass became entirely soft and sticky. More detailed procedures with respect to specific resins are given in Examples 3 and 4.

TABLE HI.-SOFTENING POINT OF RESINS FORMED FROM THE REACTION OF BIUREA AND DIOARBOXYLIO ACIDS Softening Point Range, C.

Resin formation 4hrs. additional carried out at reaction time 220-230 O. at 180=l=10 C. and 1 atm. and 656 mm.

Acid reacted with biurea no data. no data. no data. 80-90.

no data. no data. 80-90.

Sebacic T maintained at a lower temperature in the range of 170+ 190 C. under 5-6 mm. vacuum for an additional four hours. Softening points of these products were determined using the procedure described supra.

The following examples will more fully invention but should in no way limit it. m

EXAMPLE 1 Preparation of a biurea-malom'c acid resinous product Biurea 0.354 gram) and malonic acid 0.312 m were admixed with 0.0006 gram of toluene sulfonic acid (catalyst) in a Pyrextest tube and forthwith heated to a temperature in the range of about 220 to 240 C. at

atmospheric pressure by means of an oil bath. Upon attaining the aforementioned temperature range a vigorous foaming reaction occurred subsiding after about 30 minutes and resulting in a slightly yellow liquid. A clear slightly reddish-yellow resinous product formed on cooling.

EXAMPLE 2 Preparation of a biurea-azelaic acid resinous product Biurea (0.354 gram) and azelaic acid (0.564 gram) were quickly heated along with 0.0009 gram of toluene sulfonic acid as a catalyst to a temperature of 230 C. After approximately 30 minutes a clear solution formed which on cooling formed a clear resin-like solid.

EXAMPLE 3 Determination of softening point of resinous biureamalonic acid product A quantity of the novel resinous product from Exampie 1 derived from biurea and malonic acid was placed in a Pyrex test tube and slowly heated by means of an oil bath. At a temperature of C. the resinous product commenced softening and on further heating to C. the entire product became a soft, sticky mass. The temperature range between which the product started 'softening'and became completely soft, i.e., 110120 C., was designated to be the softening point range for the whole resinous biurea-malonic acid product.

EXAMPLE 4 Solubility of resinous biurea-malonic acid product Eight 0.05 gram samples of the resinous biureamalonic acid product were weighed out and deposited in separate Pyrex test tubes. To each test tube was added 1.5 ml. of one of the following solvents: dioxane, chloroform, dimethylformamide, toluene, butyl alcohol, methyl ethyl ketone, water and methyl alcohol. Each .tube at room temperature was manually shaken several describe the times and the solubility of the resinous product was recorded as soluble, slightly soluble, or insoluble. Subsequent thereto the test tubes were placed in oil baths and each tube was gradually heated to the boiling point of the respective solvent contained therein at which temperature the solubility of the biurea-malonic acid resinous product in the boiling solvent was recorded. A third recordation 0f solubility of the resinous product in each aforementioned solvent was made when the solvents were cooled back down to room temperature. As

can be seen in Table III the resinous biurea-malonic acid product was insoluble in all the aforesaidsolvents excepting water, in which the resinous product is soluble at 100 C., and slightly soluble at room temperature in dimethylformamide, wherein a suspension forms at the temperatures tested.

EXAMPLE 5 Casting a saucer ture, the mold is opened and a saucer composed of the resin is obtained. The resin can be used in the molding industry and also as a surface coating for ornamental objects. Other uses for which the novel resin is applicable are trays, bottle closures, and the like.

We claim:

l. The process of forming a resin that comprises condensing biurea with an equimolar amount of a linear saturated dicarboxylic acid having a chain length of 3-9 carbon atoms at atmospheric pressure and at a temperature in the range of about 200 to 250 C.

2. The process according to claim 1 in which toluene sulfonic acid is used as a catalyst.

3. The process according to claim 1 in which the dicarboxylic acid is malonic acid.

4. The process according to claim 1 in which the dicarboxylic acid is glutaric acid.

5. The process according to claim 1 in which the dicarboxylic acid is pimelic acid.

6. The process according to claim 1 in which the dicarboxylic acid is azelaic acid.

7. The process according to claim 1 in which the dicarboxylic acid is sebacic acid.

Moldenhauer et a1 May 30, 1944 Moldenhauer et al. June 19, 1945 

1. THE PROCESS OF FORMING A RESIN THAT COMPRISES CONDENSING BIUREA WITH AN EQUIMOLAR AMOUNT OF A LINEAR SATURATED DICARBOXYLIC ACID HAVING A CHAIN LENGTH OF 3-9 CARBON ATOMS AT ATMOSPHERIC PRESSURE AND AT A TEMPERATURE IN THE RANGE OF ABOUT 200* TO 250*C. 